Syntheses,structures, and luminescence of three 4-connected zinc coordination polymers with bis(1,2,4-triazol-1-yl)propane and benzenebiscarboxylate

Three zinc(II) coordination polymers {[Zn(btp)(1,2-bdc)(H₂O)]?·?H₂O} _n (1), {[Zn(btp)(1,3-bdc)(H₂O)]?·?1.5H₂O} _n (2), and {[Zn(btp)(NO₂-1,3-bdc)(H₂O)]?·?2H₂O} _n (3) were synthesized by 1,3-bis(1,2,4-triazol-1-yl)propane (btp) and bis-carboxylate. Compound 1 is a thick 2-D network; 2 and 3 are undulated 2-D (4,4) networks. In 2 and 3, two adjacent networks interpenetrate to form a new 2-D double-layer network, which is sustained by hydrogen-bonding interactions. Compounds 1 and 2 reveal blue emission maximum at 351 and 403, respectively, in the solid state at room temperature.     

Syntheses and crystal structures of three pillared complexes based on H2AIP and triazole-bipyridine ligands

Three pillared polymeric complexes, {[Ni₂(AIP)₂(4,4′-bpt)(H₂O)₂]·4H₂O}_n (1), {[Co(AIP)(3,3′-bpt)]·H₂O}_n (2), and {[Ni(AIP)(3,3′-bpt)]·H₂O}_n (3) (H₂AIP = 5-aminoisophthalic, 4,4′-bpt = 1H-3,5–bis(4-pyridyl)-1,2,4-triazole and 3,3′-bpt = 1H-3,5-bis(3-pyridyl)-1,2,4-triazole), have been hydrothermally synthesized and characterized by X-ray diffraction analysis. Both 1 and 3 have 2-D (6,3) honeycomb layers, which are further interlinked by bent pillared triazole-bipyridine ligands to form a bilayer structure. The structures can be simpli?ed to a (3,4)- and (3,5)-connected geometrical topology, respectively. Compound 2 has a Co-AIP layer structure in which the layers are pillared by 3,3′-bpt spacers to form the 3-D CsCl net.     

Syntheses,structures and photocatalytic degradation of organic dyes for two isostructural copper coordination polymers involving in situ hydroxylation reaction

Two copper(II) coordination polymers, {[Cu₂(btre)(hsuc)Cl(H₂O)]·1.5H₂O}_n (1) and {[Cu₂(btre)(hsuc)Br(H₂O)]·1.5H₂O}_n (2) (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane, H₃hsuc = 2-hydroxysuccinic acid), were synthesized by the hydrothermal method via in situ hydroxylation reaction with fumarate (fum), btre and CuCl₂/CuBr₂, and characterized by elemental analyses, IR, TG and X-ray diffraction. 1 and 2 are isostructural and show a 4-connected 2-D network based on [Cu₂O] dimers. 1 and 2 show good photocatalytic activity for the degradation of organic dyes methylene blue and methyl orange under UV light irradiation.     

Copper(II) coordination polymers constructed from aromatic polycarboxylate and flexible triazole ligands with different spacer lengths: syntheses,structures, and properties

{[Cu₂(btm)₂(Hbtc)(H₂btc)₂(H₂O)]·9.5H₂O}_n (1), [Cu(bte)(H₂btc)₂]_n (2) {[Cu(btp)(H₂btc)₂]·0.25H₂O}_n (3) (btm?=?bis(1,2,4-triazol-1-yl)methane, bte?=?bis(1,2,4-triazol-1-yl)ethane, btp?=?bis(1,2,4-triazol-1-yl)propane, H₃btc?=?benzene-1, 3, 5-tricarboxylic acid) have been synthesized and structurally characterized. 1 features a 1-D double chain, which is interconnected by classical hydrogen-bonding (O–H?O) and π–π interactions to lead to a 3-D supramolecular architecture. 2 and 3 are both 1-D single chains, which are interconnected by π–π interactions to 2-D layer architectures. Elemental analysis, XRD, IR, TG and EPR spectra have been carried out and discussed.     

Two independent, 1-D metal–organic nanotubes based on rings or helical chain units

Three coordination polymers {[Mn(bte)(NO₂-1,3-bdc)(H₂O)]·H₂O}_n (1), {[Mn(btp)(NO₂-1,3-bdc)(H₂O)]·2H₂O}_n (2), and {[Mn(btb)(NO₂-1,3-bdc)(H₂O)]·H₂O}_n (3) (bte, 1,2-bis(1,2,4-triazol-1-yl)ethane; btp, 1,3-bis(1,2,4-triazol-1-yl)propane; btb, 1,4-bis(1,2,4-triazol-1-yl)butane, NO₂-1,3- H₂bdc, 5-nitroisophthalic acid) were synthesized by combination of bte, btp, and btb, conformationally flexible ligands with different spacer lengths, and the rigid [NO₂-1,3-bdc]^2?. In 1, two [NO₂-1,3-bdc]^2? anions link adjacent [Mn₂(bte)₂] rings to give an independent, 1-D metal–organic nanotube (MONT). The structure of 2 is an undulating 2-D (4,4) network. In 3, the combination of a [Mn(btb)]_n single helical chain and two [Mn(NO₂-1,3-bdc)]_n linear chains assemble an intriguing independent, 1-D MONT. An interesting structural feature of 1 and 3 is that the nitro groups of each 1-D MONT interpenetrate into two adjacent 1-D MONTs to form a 1-D → 2-D interdigitated array. 3-D architectures in 1 and 3 are assembled via hydrogen bond interactions. The luminescent properties and thermal stabilities of 1, 2, and 3 were investigated.     

Syntheses,structures, and fluorescent properties of four Co(II) coordination polymers based on 5-hydroxyisophthalic acid and structurally related bis(benzimidazole) ligands

Four cobalt(II) coordination polymers, {[Co(HO-BDC)(bbp)]}_n (1), {[Co(HO-BDC)(bmbp)₂]·(H₂O)₂}_n (2), {[Co(HO-BDC)(bbb)]}_n (3), and {[Co₂(HO-BDC)₂(bmbb)₂]·(H₂O)₃}_n (4), where HO-H₂BDC?=?5-hydroxyisophthalic acid, bbp = 1,3-bis(benzimidazol-1-yl)propane, bmbp = 1,3-bis(2-methyl-benzimidazol-1-yl)propane, bbb = 1,4-bis(benzimidazol-1-yl)butane, and bmbb = 1,4-bis(2-methyl-benzimidazol-1-yl)butane, have been synthesized and characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, thermogravimetric analyses, and fluorescence properties. Compounds 1 and 3 are 4-connected 2-D networks with (4⁴·6²) topology. Compound 2 is a 1-D chain, while 4 features a 1-D ladder. These 1-D and 2-D complexes are further connected by hydrogen bonds to form 3-D supramolecular architectures. Complexes 1–4 showed very strong yellow luminescence emission.     

Synthesis,crystal structure,and properties of cobalt,zinc, and manganese coordination polymers based on fluconazole

Three complexes based on fluconazole, namely, {[Co₂(HFlu)(dpa)₂(H₂O)₂]·H₂O}_n (1), {[Zn(HFlu)(IPA)]·H₂O}_n (2), and {[Mn(HFlu)₂(IPA)(H₂O)]·H₂O}_n (3) (HFlu?=?fluconazole, 2-(2,4-difluoro-phenyl)-1,3-bis(1,2,4-triazol-1-yl)-propan-2-ol; H₂dpa?=?diphenic acid; H₂IPA?=?isophthalic acid) have been synthesized. Single-crystal X-ray analysis revealed that 1 is a 2-D-network framework containing a trinuclear Co(II) unit, 2 is a 3-D framework, and 3 is 1-D double chain structure with a Mn₂ metallocyclic core. The complexes have also been characterized by elemental analyses, IR, UV/vis and fluorescence spectroscopy, and thermal gravimetry. The phase purity of these polymers has been confirmed via powder X-ray diffraction.     

Crystal structures and luminescence of two cadmium(II) polymers constructed from aromatic polycarboxylate and bis(1,2,4-triazol-1-yl)methane ligands

Two new coordination compounds, {[Cd₂(btrm)(ip)₂(H₂O)₂]?·?2H₂O} _n (1) and {[Cd₂(btrm)(hip)₂(H₂O)₄]?·?3H₂O} _n (2) (btrm?=?bis(1,2,4-triazol-1-yl)methane, H₂ip?=?isophthalic acid, H₂hip?=?5-hydroxy isophthalic acid), have been synthesized and structurally characterized. Compound 1 is a 3-D network with CdSO₄ topology. Compound 2 contains 1-D ladder structures, which are interconnected by classical hydrogen-bonding interactions (O–H?···?O) to lead to 3-D supramolecular architectures. Luminescence was performed on 1 and 2, both of which showed strong fluorescent emissions in the solid state at room temperature.     

A 2-D tetrazole-based Zn(II) coordination polymer: crystal structure,dielectric constant,and luminescence

A tetrazole-based Zn(II) coordination polymer, [Zn(TMPT)₂] _n (1) (TMPT?=?5-(4-((1H-1,2,4-triazol-1-yl)methyl)phenyl)-2H-tetrazole), was synthesized by in situ reaction of 4-((1H-1,2,4-triazol-1-yl)methyl)benzonitrile, Zn(NO₃)_2?·?6H₂O, and NaN₃ under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. Complex 1 contains π–π stacking interactions between tetrazole rings and phenyl rings of the 2-D ordered layered structural framework, which contribute to the dielectric response. In addition, 1 was demonstrated to display strong blue fluorescence emissions in the solid state at room temperature.     

Four Co(II)/Zn(II) coordination polymers with a multidentate ligand: syntheses,structures, thermal,and photoluminescent properties

Two pairs of isostructural transition metal coordination polymers, {[Co(L)(H₂O)]_n} (1) and {[Zn(L)(H₂O)]_n} (3), {[Co(L)(4,4′-bipy)(H₂O)]·H₂O}_n (2) and {[Zn(L)(4,4′-bipy)(H₂O)]·H₂O}_n (4) (H₂L = N-pyrazinesulfonyl-glycine acid and 4,4′-bipy = 4,4′-bipyridine), have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental and thermogravimetric analyses. The structures show that 1 and 3 display 2-D polymeric grid frameworks with a 3-connected (4, 8²) topology. 2 and 4 also exhibit a 2-D polymeric grid structure, but are constructed by a 4-connected (4, 4) topology. The adjacent 2-D polymeric grid frameworks for 1–4 are further linked by hydrogen bonding O–H?O interactions to form 3-D supramolecular interweaved orderly networks. The fluorescent properties of 3 and 4 were investigated in the solid state.     

Syntheses and structures of two zinc coordination polymers with a three-dimensional α-polonium cubic network and a two-dimensional (4,4) network

Two unusual zinc coordination polymers {[Zn(bim)₃](NO₃)₂·(H₂O)₄} _n (1) and {[Zn(bte)₂ (H₂O)₂](NO₃)₂} _n (2) [bim?=?1,2-bis(imidazol-1-yl)ethane, bte?=?1,2-bis(1,2,4-triazol-1-yl)ethane] were synthesized and characterized. 1 possesses a double interpenetrating three-dimensional α-polonium cubic network and 2 consists of a two-dimensional (4,4) network.     

Syntheses, crystal structures, and magnetic and fluorescence properties of three metal complexes coordinated by mixed flexible (2-pyridylmethyl,3-pyridylmethyl)amine and rigid 5-sulfoisophthalate ligands

Three new complexes, {[Cu₃(2,3-pyma)₂(sip)₂(H₂O)₅]·5H₂O} _n , {[Zn(H-2,3-pyma)(sip)(H₂O)]·H₂O} _n , and {[Cd(H-2,3-pyma)(sip)(H₂O)]·H₂O} _n (2,3-pyma = (2-pyridylmethyl,3-pyridylmethyl)amine and H₃sip = 5-sulfoisophthalic acid) were synthesized and structurally characterized by single-crystal X-ray diffraction. The Cu(II) complex crystallizes in neutral two-dimensional layers in which the Cu(II) centers are bridged by both the flexible 2,3-pyma and the rigid sip ligands. The Zn(II) and Cd(II) complexes contain neutral one-dimensional chains linked by the rigid sip anions, whereas the flexible H-2,3-pyma ions only act as terminal ligands. The Cu(II) complex shows weak antiferromagnetic interactions, while the Zn(II) and Cd(II) complexes exhibit fluorescent emissions in the solid state.     

Syntheses,crystal structures and antibacterial activities of M(II) benzene-1,2,3-triyltris(oxy)triacetic acid complexes

Four metal(II) complexes with benzene-1,2,3-triyltris(oxy)triacetic acid (H₃L), {[Co_1.5(L)(H₂O)₆]·6H₂O}_n (1), {[Co_1.5(L)(4,4′-bipy)_1.5(H₂O)₄]·4H₂O}_n (2), {[Co(HL)(2,2′-bipy)(H₂O)₂]·1.5H₂O}_n (3), and {[Cu(HL)(phen)(H₂O)₂]·H₂O}_n (4) (4,4′-bipy = 4,4′-bipyridine; 2,2′-bipy = 2,2′-bipyridine; phen = phenanthroline), were prepared and structurally characterized. Complex 2 displays a 1-D structure, while 1, 3, and 4 reveal 0-D structures, which further extend to 3-D supramolecular networks by hydrogen bonding interactions, of which 1 and 4 contain double-helical chains, 2 includes meso-helices, and 3 comprises single-helices. Furthermore, the thermal stabilities and antibacterial activities of the complexes were studied.     

Anion-induced assembly of two distinct copper(II) coordination polymers with a versatile multidentate N-donor ligand

Reaction of a ligand N-(3,5-di-2-pyrazinyl-4H-1,2,4-triazol-4-yl)-2-pyrazinecarboxamide (Hpztp) with CuSO₄ and Cu(acac)₂ (acac = acetylacetonate), respectively, yields two distinct Cu^II coordination polymers {[Cu₃(pztp)₂(SO₄)₂(H₂O)₂]·3H₂O} _n and {[Cu(pztp)(acac)]·0.5H₂O} _n . Both complexes have been structurally determined and also characterized by physicochemical and spectroscopic methods. The results reveal that by using different anions (SO₄ ^2? versus acac^?), the dimensionality (from 2D to 1D) of the resulting coordination architectures as well as conformations and binding fashions of the pztp ligand are significantly changed. That is to say, the selection of anions will play a key role in inducing the formation of the crystalline materials. The thermal stabilities of both complexes have also been explored and discussed.     

Luminescent sensing of Fe3+ and K+ by three novel imidazole dicarboxylate-based MOFs

In this paper, three luminescent metal–organic frameworks, namely: [Zn(p-IPhHIDC)]_n (1), {[Cd(p-IPhIDC)(H₂O)]·CH₃OH}_n (2) and [Zn(p-TIPhHIDC)]_n (3), bearing two novel substituted imidazole dicarboxylate ligands, 2-(p-N-imidazol-1-yl)-phenyl-1H-imidazole-4,5dicarboxylic acid (p-IPhH₃IDC) and 2-p-(1H-1,2,4-triazol-1-yl)-phenyl-1H-imidazole-4,5dicarboxylic acid (p-TIPhH₃IDC), have been prepared and characterised through infrared spectra, X-ray powder diffraction, elemental analyses, thermogravimetric analyses and single-crystal X-ray diffraction. Ignoring the free methanol molecule and coordinated water in 2, 1–3 are similar structures. Moreover, the luminescent properties of the MOFs have been explored. It was found that MOFs 1 and 2 show good luminescent sensing of Fe³⁺ in varying degrees, and 3 of K⁺.     

杂金属杯[4]配位聚合物的合成与表征

合成了4个杂金属杯[4]配位聚合物{[Cd（L）（tpa）]·3H₂O}_n（1）,{[Zn2（L）₂（tpa）₂]·3H₂O}_n（2）,{[Co（L）（oba）]·2DMA·0.5H₂O}_n（3）和{[Zn（L）（oba）]·DMA}_n（4）（L=2-（1H-咪唑基-甲基）-6-（3-（1H-咪唑基-甲基）-5-叔丁基-2-羟基）苄基-4-叔丁基苯酚,H₂tpa=对苯二甲酸,H₂oba=4,4''-二苯醚二甲酸）,并通过元素分析、热重、红外光谱、固态紫外、单晶X射线衍射和粉末X射线衍射对其进行了表征。单晶结构分析表明晶体1是单斜晶系,P2₁/n空间群,而晶体2,3和4均为三斜晶系,P1空间群。化合物1,2,3和4是由0维[M（N₄O₂C₂₉H₃₆）]（M=Zn,Co,Cd）的杂金属杯[4]与配体对苯二甲酸和4,4''-二苯醚二甲酸形成的一维配位聚合物。     

Syntheses,crystal structures,and fluorescent properties of two 2-D Cd(II) complexes based on 2-((1H-1,2,4-triazol-1-yl)methyl)-1H-benzimidazole and 1,2,4,5-benzenetetracarboxylate

Two complexes formulated as {[Cd(btec)_0.5(tmb)H₂O]·4H₂O}_n (1) and {[Cd(H₂btec)(tmb)(H₂O)]·2H₂O}_n (2) (H₄btec?=?1,2,4,5-benzenetetracarboxylic acid, tmb?=?2-((1H-1,2,4-triazol-1-yl)methyl)-1H-benzimidazole) have been synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. Single crystal X-ray diffraction shows that 1 has a 2-D layer structure in which tmb bridges and all of the carboxylates from 1,2,4,5-benzenetetracarboxylate chelate. In 2 Cd(II) ions are bridged by monodentate carboxylates leading to a 2-D layer structure with all tmb ligands coordinated monodentate to Cd(II), hanging at two sides of the layers. Complexes 1 and 2 are further extended to 3-D supramolecular structures by hydrogen bonding interactions. Luminescent properties have been investigated in the solid state at room temperature.     

Poly­[[[(1,10‐phenanthroline‐κ2N,N′)­zinc(II)]‐μ3‐5‐hydroxy­isophthalato‐κ4O,O′:O′′:O′′′] monohydrate]

In the title compound, {[Zn(C₈H₄O₅)(C₁₂H₈N₂)]·H₂O}_n or {[Zn(OH‐BDC)(phen)]·H₂O}_n (where OH‐H₂BDC is 5‐hydroxy­isophthalic acid and phen is 1,10‐phenanthroline), the Zn atoms are coordinated by two N atoms from the phen ligands and by four O atoms from hydroxy­isophthalate ligands in a highly distorted octahedral geometry, with Zn—O distances in the range 2.042 (4)–2.085 (5) Å and Zn—N distances of 2.133 (5) and 2.137 (5) Å. The {[Zn(OH‐BDC)(phen)]·H₂O}_n infinite zigzag polymer forms a helical chain of [Zn₂(OH‐BDC)₂]_n units. Face‐to‐face π–π interactions (3.60–3.75 Å) occur between two phen rings belonging to the same helical chain. Consolidation of the packing structure is achieved by O—H⋯O hydrogen‐bonding interactions between the carboxyl­ate O atoms, the hydroxyl group and the water mol­ecule, forming two‐dimensional sheets.     

Self-Assembly of ZnII/CdII/PbII Coordination Polymers with a Tripodal Ligand Derived from Aromatase Inhibitor Letrozole Derivative

Reactions of the aromatase inhibitor letrozole derivative 4,4'-(1H-1,2,4-triazol-1-yl)methylene-bis(benzonic acid) (H₂tzmb) with Zn^II, Cd^II, or Pb^II salts under similar conditions resulted in the generation of three coordination polymers, namely, {[Zn(tzmb)(H₂tzmb)] · H₂O}_n ( 1 ), [Cd(tzmb)(H₂O)₂]_n ( 2 ), and {[Pb(tzmb)(H₂O)] · DMF}_n ( 3 ), respectively. Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, and thermogravimetric analyses. Complex 1 features a twofold 2D → 2D interpenetrated network based on corrugated 6³- hcb layers, and complex 2 exhibits a flat 2D 4.8²- fes network, whereas complex 3 presents a 3D hex net based on infinite rod-shaped secondary building units. The remarkable structural diversity may illustrate the powerful effect of metal ions on coordination assemblies. The spectroscopic, thermal, and photoluminescent properties of complexes 1 – 3 were investigated. In addition, the catalytic activity of 1 in the solvent-free ring-opening polymerization of ε-caprolactone was also discussed.     

Synthesis,crystal structures,and photocatalytic properties of two 2D supramolecular silver(I) coordination polymers derived from bis(1,2,4-triazole) and aromatic dicarboxylate ligands

Two silver(I)-mixed ligand coordination polymers (CPs), {[Ag(L)(Hmip)]·H₂O} _n (1) and {[Ag(L)]·0.5(DCTP)·H₂O]} _n (2) (H₂mip = 5-methylisophthalic acid, H₂DCTP = 2,5-dichloroterephthalic acid, and L = 4,4′-bis(1,2,4-triazol-1-ylmethyl)biphenyl) have been hydrothermally synthesized and structurally characterized. Two CPs display 1D zigzag chain and linear chain structures, respectively. Furthermore, these 1D chains are extended into 2D supramolecular networks through hydrogen bonding interactions. The luminescence properties and photocatalytic behaviors of both CPs are reported.